Dye preparation



Patented June. 2, 1936 DYE PREPARATION Wolf Kritchevsky, Chicago, 111.,assignor to Bit Products Corporation, Chicago, 111., a corporation ofIllinois No Drawing. Application December 9, 1932,

Serial No. 646,496

10 Claims.

- the same.

It iswell understood that the art of dyeing fabricsis an exceedinglycomplicated and technical business. Regularly established dyeingindustries are equipped to make use of all of the known chemicals,assistants, mordants and the like which the industry possesses; as wellas all of the equipment for turning out-a first class result independentof the type of material or color. The home dyer has none of thefacilities available to the regular dyeing establishments and so a dyemust be placed in his hands which, with the limited experience andability available to the amateur dyer, will turn out a first classproduct on all types of materials. The development of a dye for homeuse, therefore, is an exceedingly technical problem because the dye musthave characteristics which the skilled dyer would never expect in hisown product.

There has been an extensive development of dyes for home use. The socalled soap dyes were one of the early developments along this line.These took on different forms, all attempting to improve the product.The soap dyes have employed assistants with them such as sulphonatedoils and other materials along this general line. Besides taking aconsiderably long time to dissolve, they possessed other disadvantagesat times, well known to those skilled inthe'jart. Applicants priorPatent No. 1,752,184 represented a development which was a great stepforward in the art and consisted of substituting for the soap in thesoap dye a material which would function as a soap in its desirableproperties but which would avoid the disadvantages attending the use ofsoap. The resulting product had excellent solubility, proper leveling;it did not precipitate out in the presence of hard water as soap did.The principal disadvantage of this product, however, was that afterdyeing with it the garments did not have the proper finish and theproper feel. -In otherlwords, the garment so dyed did not have theappearance of a new garment,

which is one of the features expected in a newly dyed piece of fabric.It is well knownthat this finish and feel can be obtained in part fromthe use of \an oleaginous material in the dye bath, such as asulphonated oil or similar ole'aginous substance, it being known thatthe more oleaginous the product, the greater the improvement insofar asthe finish and feel. .I attempted to improve the dye product produced inaccordance with the above mentioned patentby employing a mixture ofsulphonated alkylated polynuclear hydrocarbons and the compound havingfatty properties such as sulphonated oil or a sulphonated soap. I foundthat-this was impossible in a practical way because the presence of theoily 5 material seemed to deprive the product of the desirablecharacteristics obtained by the use of the wetting agent. In otherwords, the resulting dye no longer dissolved readily and possessed someof the same disadvantages attending the 10 use of ordinary soap dyes. Inspite of all of the developments, 1 still found that there was difiiculty due to the forming of lime salts and the disadvantage of not beingable to work in a slightly I acid medium, which is preferable for mostdyeing. 15

with this knowledge of the art before me, it was my object to produce animproved dye for home use which would have all of the advantages of suchdyes heretofore used but would also avoid all of the disadvantagesthereof.

Another object is the provision of an improved dye for home use adaptedto be employed with different types of fabrics.

Another object is to place a packaged dye in the hands of the ordinaryhousewife which will 25 permit her substantially to duplicate theresults obtained in the most up-to-date dyeing establishments.

Other objects and features of the invention will be apparent as thedetailed description so progresses.

vIn developing my improved product, Iproceed-' ed on the assumption thatthe carboxyl group in some of the compounds, soaps, sulphonated oil,etc., employed in home dyes was undesirable-for the reason that it formsinsoluble precipitates with calcium and magnesium salts found in hardwater. This was not a new concept as I knew that considerable work hadbeen done either to replace the carboxyl group with another group 40 orto combine it chemically with some other compound or compounds so thatit would not exert its harmful effect. In sulphonated oils, the carboxylgroup is in the form of a glyceride, but being a tri-glyceride, theratioof the esterifying alcohol to the total amount of the carboxyl groups is'not sufilcient to keep it stable and for this reason when heated withwater it hydrolyzes and forms lime salts and insoluble greases. A greatadvance was made by the realization that when the carboxyl group isesterified with a mono.- valent or polyvalent alcohol or amidized withammonia or an amine or their substitutionproducts, the resultingproducts become stable. vl'n the case of the polyvalent alcohols, notall the use without having to use additional wetting agents of the typerequired previously.

To describe such compounds, I wish to cite the following references:Monovalent alcohol esters of a. sulphonated oil are the butyl ester orbenzyl ester of sulphonated oleic acid as described in the United StatesPatent No. 1,822,977, Example Three; two other Patents 1,822,978 and1,822,979

describe similar compounds and methods of making them. These compoundscan be made by esterifying a sulphonated fatty acid or by sulphonatingan esterified fatty acid which is esterified with a monovalent alcohol.

Amids of sulphonated-fatty acids can be characterized by the followingcompounds:

(a) Sulphonated stearyl amid of the formula- I SOzNa I C ioHazCH-C O-NH:Y and the alkyl and aryl substitution product thereof like benzylstearyl amid sulphonic acid SOaNa omwn-oormcmcm, etc. (to Sulpholeilamid of the formula 11 s4(OSO Na)CONH In the" case where divalentalcohols are used like ethylene glycol, diethylene glycol or trivalentalcohol like glycerol, then at least one of the hydroxy groups shouldremain free or positively sub-'- stituted and preferably two. In otherwords, if

. sulpholeic acid is esterified with ethylene glycol,

diethylene. glycol or glycerol leaving one of the hydroxy groups of theglycol free or positively substituted or one or two of the hydroxygroups of glycerol free or positively substituted, desirable compoundsare obtained. These compounds can also be made by first esterifying thefatty acid and making compounds like monostearyl glycol or monoleylglycol or monostearyl glycerol or distearyl glycerol and thensulphonating the ester where the sulphuric acid group will go into thefatty acid nucleus or preferably form an ester with the hydroxy group.Phosphoric acid esters can be made which are just as eflicient. Toillustrate, I wish to' refer to German Patent No. 193,189 where the.distearyl glycerol phosphoric acid ester is described. Another compoundbelonging to the same class is the mono-oleyl ethylene glycolsulphonated as described in French Patent No. 721,340, Example 1.

The compounds described in the above paragraph are esters of alcoholsand sulphuric or phosphoric acid. An advance in this was made in theUnited States Patent No. 1,881,172in which case the acidic group is tieddirectly to the car,- bon atom of the esterified alcohol giving asulphonic acid group. 4 In this case fatty acid'esters of ethanesulphonic acid are obtained .of the general formula- 1 L Rcoocnhsom Inother words, fatty acid productsof ethionic acid are obtained. Thosecompounds have all the desirable properties like wetting, stability inlime water and slightly acid solutions and also give the proper finishto textiles.

Along with the line of development of making the carboxyl group harmlessthrough 'est'eriflca- I tion or amidization. another method was devisedwhich is proving to be commercially very successful and scientificiallycorrect, viz: the carboxyl group is reduced to analcoholic group and thecorresponding alcohol sulphated or phos-- phated.

In the industry, lauric acid has been successare excellent penetratingagents, emulsifying agents, and also finishing materials. They are knownin commerce under the name of Gardinols, Avirols, etc.

The development in the last line of work has brought back to lifeanother class of substances which, from the viewpointof the chemical andphysical action, replace soap with great advantage but were neverconsidered commercially in view of the fact that the matterof'preparation 1 was too involved and they could not be obtained ineither commercial quantities nor at prices in which they could beserious competitors to soap. I am referring in this case to the straightsulphonic acid of aliphatic hydrocarbons having a chain of eight carbonatoms or more. A representative of this class is cetyl sulphonic acidand its salts which were described in greatdetail by Reychler in theKolloidale Zeitschrift, volume 12, page 2'77, in 1913. This compound is.very soluble in water in the form of its free acid or salts, gives anexcellent foam, penetrates well, and has fatty characteristics. It wasof no commercial value until lately and Prof. Schrauth has published anarticle in the Chemik'er Zeitung for 1931, page 1984, in which he statesthat when sulphuric esters of aliphatic alcohols are treated with sodiumsulphite, the sulphonic acids of the corresponding hydrocarbons can beobtained in good commercial quantities. This work was further followedup and described in English Patent No. 358,583, in which caseunsaturated hydrocarbons with a chain of notless than eight carbon atomsare sulphonated, in which casetrue sulphonic acids are formed and thenext carbon to the carbon that has thev sulphonic acid group on it has ahydroxy group. As one product I can quote the hydroxyoctadecyl sulphonicacid of the formula- CH1(CH2) 15CHOHCH2SO3H which was described inExample One of the above named patent. While all those above namedchemicals will fall into a certain number of chemical groups dependingupon their structure, yet from the viewpoint of the physical behavior,especially in regard to my application of them, they are all to beconstrued as one class.

Chemicallywe may say those substances are either sulphonic or phosphonicderivatives of long chain aliphatic hydrocarbons or theyare sulphuric orphosphoric acid esters or for that matter esters of oxygenated inorganicacids of long chain aliphatic alcohols} or, sulphuric or phosphoric acidderivatives or for that matter derivatives of oxygenated inorganic acidsof amids of higher aliphatic fatty acids and their derivatives oresters-of higher aliphatic acids esterifled in the carboxyl group eitherwith monovalent alcohols or polyvalent alcohols in which not all of thehydroxy groups are esterifled with carboxylic acids.

on the other hand, from a physical ,viewpoint and from a viewpoint ofapplication, they have the following in common:-They are chemicalshaving polar and non-polar groups connected together in the samemolecule in a very balanced ratio in which the non-polar group isstrongly oleophilic due to the fact that it has a chain of at leasteight carbon atoms or more and has affinity for fats, oils, or differentorganic compounds. The polar group is a strong oxygenated inorganic acidthat makes the compound as a whole'strongly hydrophilic, makes thecompound easily soluble in water and thereby the whole compound as'suchbecomes a very good penetrating agent, an ideal emulsifier, being in aposition to disperse fats andgreases in water and give a fatty feel tocompounds with which it is penetrated from a purely water medium.

In the above description I have given an idea of the different classesof compounds and representative examples that are suitable for mypurpose. I have done it only for the purpose of teaching the art to theextent where it would be easy for any qualified chemist to arrive atother classes of the same general characteristics.

In general, I found that the proper types of compounds that arenecessary for my purpose must be quite soluble by forming a truesolution or colloidal solution or form at least a very fine stabledispersion in water without precipitating with other agents under anycondition in which they maybe used. In other words, the compoundemployed must be strongly hydrophilic and have great penetrating valuebut at the same time it must also possess oleophillc properties to thepoint commercially known as Gardinol WA 70 commonsalt. I

j Example 2 Per cent 5 of cyanone blue 5R,-color index #289 5 directblue BB, color index #406 90 of the sodium salt of the sulphuric acidester of oleyl alcohol of the general formula otherwise known asGardinol CA Example 3 Per cent 1 25 of direct green, color index #593 5of chrystophenin, index #365 25 of the sodium salt of the sulphuric acidester .of cetyl alcohol of the general formula C1sHa1CH-.--0--SO3N9.

otherwise known. as Avirol 142 ammonium sulphate Example 4 Per cent 3 ofmethylene blue, color index #922 3 of sodium salt of the sulphuric acidester'of reduced coconut oil fatty acids, commercial- 5 ly known asGardinol' R 94 dextrine.

Example 5 Per cent 5 acid rhodamine 3R, Manual 534 5 sodium cetylsulphonate 45 alcohol 45 glycerin Example 6 Per cent 20 Catechu G N,color index 420 3 hydroxy-octadecyl-sulphonic acid, general formula 4Gila-(CH2) 15CHOH-CH2-SO3NG 77 ammonium sulphate I I Example? Percent I30 alizarine blue, color index #1054 15 sodium salt of the sulfationproduct monooleyl ethylene glycol of the formulaC1-1Haa'C0-OCH2CH=OSOaNa 55 common salt Example 8 Percent 5 of cyanoneblue 5R, color index #289 5 direct blue BB,-color index #406 15 of thesodium salt of the sulphuric acid ester of oleyl alcohol of the generalformula otherwise known as Gardinol CA 75 of Glauber salt a Example 9Percent 10 pontamine bordeaux B, color index #375 9 cyanine blue 5R,color index #289 20 dark blue BH, color index #401 11 sodium salt ofricin'oleic acid of ethionic acid of the general formula C11H32 (OH)COO-C2H4SO3Na Glauber salt Example 10 Percent 20 algol scarlet G, colorindex #112 20 benzyl ester of sulpholeic acid of the general formula tCrzHadOSOsNa) COOCHzCsH:

10 of sodium hydroxide 20 of sodium hydrosulphite 30 of sodium carbonateExample 11 Percent 10 of lithol rubin BN, color index #163 10 of thesalt of the phosphoric acid ester distearyl glycerin of the formulacnHacoo-cm-cmococnmn CHzO-PO(ONa)z 10 soda ash Glauber salt g,

Example 12 Percent 10 chrysamine, C. I. 365 10 of sulphonated oleylamide of the general formula CnHmOSOaNa) CONH:

80 salt so I Percent Example 13 10 pontamine bordeaux B, color index#375 10 lecithin 20 salt 60 sugar.

' phosphoric acid group or similar groups. They must have an excellentwetting out action, should preferably dissolve completely in water, maketrue or colloidal solutions or at least disperse completely to formstable dispersions. They must also have properties that will give thearticle with which they are distributed stability and give it some oilyfeel which is accomplished by these particular chemicals having an alkylgroup of not less than eight carbon atoms or its derivatives likehydroxy, halogen derivatives, acidic derivatives. They also may have'anaralkyl group, the alkyl group still not having less than seven carbonatoms.

- It will be noted that this general formula will take in any of thecompounds discussed previously in the specification and define it to thepoint where everyone skilled in the art will be able to use it as aguide for his work.

The degree of the oleophilic properties of these compounds can beregulated by the length of the hydrocarbon chain. Those from Cs -up toCu have the oleophilic properties not as pronounced as those beginningwith Cu, and depending upon thedesirability of the degree of oilinessrequired those compounds can be chosen to suit the product, but it mustbe understood that in no case can tltigl iiroduct be useful unless it isstill quite hydro- D In describing the invention, it is understood thatthe examples and illustrations given are to be taken in a descriptivesense rather than ins. limiting sense, Asfar as the specific examples ofthe dye products are concerned, these are meant to show different typesof wetting and combining agents expressed by the general formula.

I have referred 'hereinabove to the solubility of the class of chemicalswhich I employ by stating that they should be freely soluble,colloidally soluble or form very fine dispersions in aqueous media. Theterms "soluble and solubility as employed in the claims, therefore, areused in the broadest sense to refer either-to true solutions or tocolloidal solutions or very fine dispersions which as far as my purposeis concerned have substantially the same fimction as true solutions. Itshould also be borne in mind that many terms employed in thespecification are used in a descriptive sense rather than in a limitingsense and the details are given for illustration so that those skilledin the art may be able to practice the invention. The novelty is definedin the appended claims. Water soluble as employed in the claims is usedin abroad sense to include the characteristics of either molecular orcolloidal dispersibility.

acid ester of an aliphatic alcohol having a chain of not less than eightcarbon atoms, said dye composition possessing the properties ofimparting an oily" feel to fabrics dyed therewith and .producing even,level shades under any of the conditions normally encountered in hornedyeing operations.

2. A home dye compomtion in solid form comprising an intimate admixtureof a normally water-soluble dye and a salt of an inorganic oxygenatedacid ester of an aliphatic alcohol having a chain of not less than eightcarbon atoms said dye composition possessing the properties of impartingan oily feel to fabrics dyed there-- with and producing even, levelshades under any of the conditions normally encountered in home dyeingoperations.

3. A home dye composition in solid form com-- prising an intimateadmixture of a normally water-soluble dye and a sulphuric acid ester ofan aliphatic alcohol having a chain of not less than eight carbon atoms,said dye composition possessing the properties of imparting an "oily"feel to fabrics dyed therewith and producing even, level shades underany of the conditions normally encountered in home dyeing operations.

4. A home dve composition in solid form comprising an intimate admixtureof a normally water-soluble dye and a salt of a sulphuric acid ester ofan aliphatic alcohol having a chain of not less than eight carbon atoms,said-dye composition possessing the properties of imparting an oily"feel to fabrics dyed therewith and producing even, level shades underany of the conditions normally encountered in home dyeing operations.

5. A home dye composition in solid form comprising an intimate admixtureof a normally water-soluble dye and a salt having the general formula-CnHQHICM-SOZX water-soluble dye and the sulphuric acid ester of laurylalcohol, said dye composition possessing the properties of imparting anoily feel to fabrics dyed therewith and producing even, level shadesunder any of the conditions normally encountered in home dyeingoperations.

7. A home dye composition in solid form com prising an intimateadmixture of a normally water-soluble dye and the sodium salt of thesulphuric acid ester of lauryl alcohol, said dye composition possessingthe properties of imparting an "oily" feel to fabrics dyed therewith andproducing even,-level shades under any of the conditions normallyencountered in home dyeing operations.

,8. A home dye composition in solid form comprising an intimateadmixture of a water-soluble dye and a salt of theisulphuric acid esterof clay] alcohol, said dye composition possessing the properties ofimparting an "oily feel to fabrics dyed therewith and producing even,level shades under any of the conditions normally encountered in homedyeing operations.

9. A home dye composition in solid form comprising an intimate admixtureof a normally water-soluble dye and an inorganic oxygenated acid esterof cetyl alcohol, said dye composition possessing the properties ofimparting an oily feel to fabrics dyed therewith and producing 'i even,level shades under any of the conditions normally encountered in homedyeing operations.

10. A home dye composition in substantially solid form comprising anintimate admixture of a normally water-soluble dye and a sulphuric acidester of oleyl alcohol wherein the sulphuric acid group is esterifiedwith the hydroxy group of the oleyl alcohol, said dye compositionpossessing the properties of imparting an oily feel to fabrics dyedtherewith and producing even, level shades under any of the conditionsnormally 5 encountered in home dyeing operations.

wow KRI'ICHEVSKY.

